Evaluation of Phosphorus Enrichment in Groundwater by Legacy Phosphorus in Orchard Soils with High Phosphorus Adsorption Capacity Using Phosphate Oxygen Isotope Analysis.

Long-term phosphorus (P) fertilization results in P accumulation in agricultural soil and increases the risk of P leaching into water bodies. However, evaluating P leaching into groundwater is challenging, especially in clay soil with a high P sorption capacity. This study examined whether the combination of PO4 oxygen isotope (δ18OPO4) analysis and the P saturation ratio (PSR) was useful to identify P enrichment mechanisms in groundwater. We investigated the groundwater and possible P sources in Kubi, western Japan, with intensive citrus cultivation. Shallow groundwater had oxic conditions with high PO4 concentrations, and orchard soil P accumulation was high compared with forest soil. Although the soil had a high P sorption capacity, the PSR was above the threshold, indicating a high risk of P leaching from the surface orchard soil. The shallow groundwater δ18OPO4 values were higher than the expected isotopic equilibrium with pyrophosphatase. The high PSR and δ18OPO4 orchard soil values indicated that P leaching from orchard soil was the major P enrichment mechanism. The Bayesian mixing model estimated that 76.6% of the P supplied from the orchard soil was recycled by microorganisms. This demonstrates the utility of δ18OPO4 and the PSR to evaluate the P source and biological recycling in groundwater.

Global scale identification of catchments phosphorus source shifts with urbanization: A phosphate oxygen isotope and Bayesian mixing model approach.

Different scenarios of urban expansion can influence the dynamic characteristics of catchments in terms of phosphorus (P). It is important to identify the changes in P sources that occur during the process of urbanization to develop targeted policies for managing P in catchments. However, there is a knowledge gap in quantifying the variations of potential P sources associated with urbanization. By combining phosphate oxygen isotopes from global catchments with a Bayesian model and the urbanization process, we demonstrate that the characteristics of potential P sources (such as fertilizers, urban wastewater, faeces, and bedrock) change as urban areas expand. Our results indicate that using phosphate oxygen isotopes in conjunction with a Bayesian model provides direct evidence of the proportions of potential P sources. We classify catchment P loadings into three stages based on shifts in potential P sources during urban expansion. During the initial stage of urbanization (urban areas < 1.5 %), urban domestic and industrial wastewater are the main contributors to P loadings in catchments. In the mid-term acceleration stage (1.5 % ≤ urban areas < 3.5 %), efforts to improve wastewater treatment significantly reduce wastewater P input, but the increase in fertilizer P input offsets this reduction in sewage-derived P. In the high-level urbanization stage (urban areas ≥ 3.5 %), the proportions of the four potential P sources tend to stabilize. Remote areas bear the burden of excessive P loadings to meet the growing food demand and improved diets resulting from the increasing urban population. Our findings support the development of strategies for water quality management that better consider the driving forces of urbanization on catchment P loadings.

Near-infrared reflectance spectroscopy accurately predicted isotope and elemental compositions for origin traceability of coffee.

Stable isotope ratios and trace elements are well-established tools that act as signatures of the product's environmental conditions and agricultural processes; but they involve time, money, and environmentally destructive chemicals. In this study, we tested for the first time the potential of near-infrared reflectance spectroscopy (NIR) to estimate/predict isotope and elemental compositions for the origin verification of coffee. Green coffee samples from two continents, 4 countries, and 10 regions were analysed for five isotope ratios (δ13C, δ15N, δ18O, δ2H, and δ34S) and 41 trace elements. NIR (1100-2400 nm) calibrations were developed using pre-processing with extended multiplicative scatter correction (EMSC) and mean centering and partial-least squares regression (PLS-R). Five elements (Mn, Mo, Rb, B, La) and three isotope ratios (δ13C, δ18O, δ2H) were moderately to well predicted by NIR (R2: 0.69 to 0.93). NIR indirectly measured these parameters by association with organic compounds in coffee. These parameters were related to altitude, temperature and rainfall differences across countries and regions and were previously found to be origin discriminators for coffee.

Using a Multi-isotope Approach and Isotope Mixing Models to Trace and Quantify Phosphorus Sources in the Tuojiang River, Southwest China.

Identifying phosphorus (P) sources is critical for solving eutrophication and controlling P in aquatic environments. Phosphate oxygen isotopes (δ18Op) have been used to trace P sources. However, the application of this method has been greatly restricted due to δ18OP values from the potential source having wide and overlapping ranges. In this research, P sources were traced by combining δ18Op with multiple stable isotopes of nitrogen (δ15N), hydrogen (δD), and dissolved inorganic carbon (δ13C). Then, a Bayesian-based Stable Isotope Analysis in R (SIAR) model and IsoSource model were used to estimate the proportional contributions of the potential sources in the Tuojiang River. δ18Op was not in equilibrium with ambient water, and statistically significant differences in the δ18Op values were found between the potential sources, indicating that δ18Op can be used to trace the P sources. δ15N, δD, and δ13C could assist δ18Op in identifying the main sources of P. The SIAR and IsoSource models suggested that industrial and domestic sewage was the largest contributor, followed by phosphate rock and phosphogypsum and agricultural sewage. The uncertainty of the calculation results of the SIAR model was lower than that of the IsoSource model. These findings provide new insights into tracing P sources using multiple stable isotopes in watersheds.

Tracing the Transformation and Allocation of the Newly Applied-P in Calcareous Soil Using an Enriched Oxygen Isotope Labeling Technique.

Different phosphorus (P) fertilizations significantly impact the transformation of the applied-P in soils. However, knowledge about how different P fertilization regimes influence the allocation of the amended-P in soil remains incomplete. Herein, we carried out a pot experiment to explore the fate of applied-P in calcareous soil using an oxygen isotope labeling technique (18O-P18O43-). Treatments included check (CK), single, and repeated applications. The phosphorus mass balance result showed that more than 48.5% of the applied-P was held in labile and moderately labile fractions with the repeated treatment, while approximately 27.4% of the added-P was recovered in nonlabile forms in the single application treatment. The isotopic tracer (18O-P18O43-) result demonstrated that the δ18OP values of NaHCO3-P and NaOH-P in the repeated P application were significantly higher than those in the single P application. Ultimately, better agronomic performances of the crops and higher PUE were achieved in the repeated treatment. Our findings highlighted that repeated P fertilization can improve P availability by reducing P fixation. These results pronounced that the enriched oxygen isotope technique can be considered an effective approach for tracing applied-P in soils.

A new sampling method with zirconium-loaded resin for phosphate oxygen isotope analysis in oligotrophic freshwater systems.

RATIONALE: The phosphate oxygen isotope ratio ( δ 18 O PO 4 ) is a useful technique to trace the sources and biogeochemical cycles of phosphorus (P) in aquatic ecosystems. However, δ 18 O PO 4 has not been widely used in oligotrophic freshwater systems due to technical and methodological difficulties in collecting sufficient phosphate (PO4 ) for the δ 18 O PO 4 analysis, which sometimes requires hundreds of liters of the water sample. In this study, a new approach (PaS-Zir) was developed for the δ 18 O PO 4 analysis in oligotrophic freshwater systems using zirconium (Zr)-loaded (ZrIRC) resin, which has a high affinity for PO4 . METHODS: ZrClO2 was added to Amberlite IRC748 to obtain the ZrIRC resin. The adsorption/desorption experiment using KH2 PO4 with a known value of δ 18 O PO 4 was conducted to determine the adsorption/desorption properties of the resin and the likelihood of isotopic fractionation. By installing mesh bags filled with the resin, the PaS-Zir approach was used in two rivers with low PO4 concentrations (0.2 and 5.3 µmol/L). A conventional sampling method was also performed in the study river with a higher PO4 concentration to validate the efficacy of the PaS-Zir method. RESULTS: The adsorption/desorption experiment demonstrated that the ZrIRC resin possessed a sufficient adsorption capacity (153 µmol/resin-mL) and exhibited little isotopic fractionation during the adsorption/desorption processes. Using the PaS-Zir method, we were able to collect sufficient PO4 samples for the δ 18 O PO 4 analysis from the rivers within at least 4 days of mesh bag installation. The δ 18 O PO 4 values (14.2‰ ± 0.2‰) obtained using the PaS-Zir method were comparable to those obtained using the conventional method (14.0‰ ± 0.03‰). CONCLUSION: We proved that the PaS-Zir method is applicable to oligotrophic freshwater systems and is generally more efficient than the conventional method. In addition, our method is useful for improving the understanding of the P dynamics of oligotrophic ecosystems because of the extremely low concentration of PO4 commonly found in them, which are often prone to P pollution.

A new method for phosphate purification for oxygen isotope ratio analysis in freshwater and soil extracts using solid-phase extraction with zirconium-loaded resin.

RATIONALE: Phosphate (PO4 ) oxygen isotope (δ18 OPO4 ) analysis is increasingly applied to elucidate phosphorus cycling. Due to its usefulness, analytical methods continue to be developed and improved to increase processing efficiency and applicability to various sample types. A new pretreatment procedure to obtain clean Ag3 PO4 using solid-phase extraction (SPE) with zirconium-loaded resin (ZrME), which can selectively adsorb PO4 , is presented and evaluated here. METHODS: Our method comprises (1) PO4 concentration, (2) PO4 separation by SPE, (3) cation removal, (4) Cl- removal, and (5) formation of Ag3 PO4 . The method was tested by comparing the resulting δ18 OPO4 of KH2 PO4 reagent, soil extracts (NaHCO3 , NaOH, and HCl), freshwater, and seawater with data obtained using a conventional pretreatment method. RESULTS: PO4 recovery of our method ranged from 79.2% to 97.8% for KH2 PO4 , soil extracts, and freshwater. Although the recovery rate indicated incomplete desorption of PO4 from the ZrME columns, our method produced high-purity Ag3 PO4 and accurate δ18 OPO4 values (i.e., consistent with those obtained using conventional pretreatment methods). However, for seawater, the PO4 recovery was low (1.1%), probably due to the high concentrations of F- and SO4 2- which interfere with PO4 adsorption on the columns. Experiments indicate that the ZrME columns could be regenerated and used repeatedly at least three times. CONCLUSIONS: We demonstrated the utility of ZrME for purification of PO4 from freshwater and soil extracts for δ18 OPO4 analysis. Multiple samples could be processed in three days using this method, increasing sample throughput and potentially facilitating more widespread use of δ18 OPO4 analysis to deepen our understanding of phosphorus cycling in natural environments.

Tracing the sources of phosphorus in lake at watershed scale using phosphate oxygen isotope (δ18OP).

Phosphorus (P) is normally considered as the limited nutrient for shallow freshwater lakes and can potentially trigger eutrophication on account of high concentrations. Due to the various transportation and transformation processes, P source apportionment and management in lake ecosystems have become more and more difficult. Combining with sequential extraction of P fractions and mineralogical analysis, the isotopic compositions of oxygen in phosphate (δ18OP) of resin-extractable P from the different samples including soil, estuary sediments, pond sediments, and lake sediments in the Shijiuhu Lake catchment, China, were investigated. The results showed that δ18OP values ranged from +15.23 to +21.92‰ in agricultural soil, +16.53 to +24.10‰ in estuary sediments, +18.90 to +20.90‰ in pond sediments, and +17.42 to +19.70‰ in lake sediments. Isotopic signatures indicated that chemical fertilizers with heavier δ18OP values (+20.70 to +26.50‰) were the predominant contributors of P in the soil. The river transportation together with Fe/Al-P desorption on anaerobic condition simultaneously stimulated the enrichment of P in the lake sediments, even though the biotic activity regulated the isotope values moving toward the equilibrium. Eroded soil was the important source of P in lake and pond sediments via drainage and runoff, and conserved the source isotope signal in the samples. Stronger biotic activity in the aquatic environments dragged δ18OP values toward the equilibrium. However, conspicuous off-equilibrium isotope signature suggested the terrestrial sources in the aquatic ecosystems. The calculation of two end-member linear mixing models suggested that soils also predominantly controlled the P occurrence in the lake sediments with contribution higher than 80%, indicating that decreasing inputs from the agricultural activities is important in P reduction on catchment scale. Generally, δ18OP from different sources can provide indirect and important evidences for the identification and management of P sources in the lake catchment.

Assessment of rapid low-cost isotope (δ15 N, δ18 O) analyses of nitrate in fruit extracts by Ti(III) reduction to differentiate organic from conventional production.

RATIONALE: The isotopic composition (δ15 N, δ18 O) of nitrate in fruits and vegetables differentiates organic from conventional food production practices. Organic systems do not use synthetic nitrate fertilizers high in 18 O and low in 15 N and thereby help reveal producers' fertilization claims. Isotope analyses of nitrate extracted from fruits and vegetables are done by bacterial reduction which is costly and by specialized laboratories. Rapid, low-cost methods are needed to promulgate nitrate isotope analyses of food products to support organic food product certification and to verify the authenticity of production claims. METHODS: Fresh strawberry samples were obtained from certified organic and conventional growers in Andalucía, Spain. We applied a new, rapid, one-step Ti(III) reduction method to convert the nitrate from strawberry extracts to N2 O gas for headspace isotope analyses using isotope-ratio mass spectrometry. Using the Ti(III) reduction method, 70 samples, controls and references were prepared and analyzed for NO3 - , δ15 N and δ18 O per 48 h. We also analyzed extracts and solids for anions and cations and for bulk δ15 N for multivariate chemometric evaluation. RESULTS: The Ti(III)-based isotope analyses of nitrate in strawberry extracts revealed clear differentiation between organic and conventional production with mean δ18 O and δ15 N values of +18.3 ± 1.2 ‰ and +17.6 ± 1.2 ‰ versus +28.2 ± 4.5 ‰ and +14.9 ± 3.0 ‰, respectively. The δ15 N of strawberry dry mass differed slightly (+3.0 ± 1.4 ‰ versus +4.0 ± 1.4 ‰) between organic and conventional samples, respectively. Chemometric analyses of nitrate isotopes and extract chemistry revealed that the δ18 O of nitrate along with δ15 N and Ca2+ fully differentiated organic from conventional strawberry production. CONCLUSIONS: Our results show the Ti(III) reduction method provides a new low-cost and rapid analytical method to facilitate compound-specific δ15 N and δ18 O isotope analyses of nitrate in selected fruit types, and likely other food products, for the purposes of assessing nitrate fertilization practices of organic versus conventional production claims and to support authenticity investigations.

Isotopic evidence for geographic heterogeneity in Ancient Greek military forces.

Increased mobility and human interactions in the Mediterranean region during the eighth through fifth centuries BCE resulted in heterogeneous communities held together by political and cultural affiliations, periodically engaged in military conflict. Ancient historians write of alliances that aided the Greek Sicilian colony Himera in victory against a Carthaginian army of hired foreign mercenaries in 480 BCE, and the demise of Himera when it fought Carthage again in 409 BCE, this time unaided. Archaeological human remains from the Battles of Himera provide unique opportunities to test early written history by geochemically assessing the geographic origins of ancient Greek fighting forces. We report strontium and oxygen isotope ratios of tooth enamel from 62 Greek soldiers to evaluate the historically-based hypothesis that a coalition of Greek allies saved Himera in 480 BCE, but not in 409 BCE. Among the burials of 480 BCE, approximately two-thirds of the individuals are non-local, whereas among the burials of 409 BCE, only one-quarter are non-local, in support of historical accounts. Although historical accounts specifically mention Sicilian Greek allies aiding Himera, isotopic values of many of the 480 BCE non-locals are consistent with geographic regions beyond Sicily, suggesting Greek tyrants hired foreign mercenaries from more distant places. We describe how the presence of mercenary soldiers confronts prevailing interpretations of traditional Greek values and society. Greek fighting forces reflect the interconnectedness and heterogeneity of communities of the time, rather than culturally similar groups of neighbors fighting for a common cause, unified by "Greekness," as promoted in ancient texts.

Assessment of multiple stable isotopes for tracking regional and organic authenticity of plant products in Hesse, Germany.

As demand for regional and organically produced foodstuff has increased in Europe, the need has arisen to verify the products' origin and production method. For food authenticity tracking (production method and origin), we examined 286 samples of wheat (Triticum aestivum), potatoes (Solanum tuberosum), and apples (Malus domestica) from different regions in Germany for their stable isotope compositions of oxygen, hydrogen, carbon, nitrogen and sulphur. Single-variate authentication methods were used. Suitable isotope tracers to determine wheat's regional origin were δ18O and δ34S. δ13C helped to distinguish between organic and conventional wheat samples. For the separation of the production regions of potatoes, several isotope tracers were suitable (e.g. δ18O, δ2H, δ15N, δ13C and δ34S isotopes in potato protein), but only protein δ15N was suitable to differentiate between organic and conventional potato samples. For the apple samples, 2H and 18O isotopes helped to identify production regions, but no significant statistical differences could be found between organically and conventionally farmed apples. For food authenticity tracking, our study showed the need to take the various isotopes into account. There is an urgent need for a broad reference database if isotope measurements are to become a main tool for determining product's origin.

Tracing uptake and translocation of phosphorus in wheat using oxygen isotopes and mathematical modelling.

Understanding P uptake in soil-plant systems requires suitable P tracers. The stable oxygen isotope ratio in phosphate (expressed as δ18 OP ) is an alternative to radioactive labelling, but the degree to which plants preserve the δ18 OP value of the P source is unclear. We hypothesised that the source signal will be preserved in roots rather than shoots. In soil and hydroponic experiments with spring wheat (Triticum aestivum), we replaced irrigation water by 18 O-labelled water for up to 10 d. We extracted plant inorganic phosphates with trichloroacetic acid (TCA), assessed temporal dynamics of δ18 OTCA-P values after changing to 18 O-labelled water and combined the results with a mathematical model. Within 1 wk, full equilibration of δ18 OTCA-P values with the isotope value of the water in the growth medium occurred in shoots but not in roots. Model results further indicated that root δ18 OTCA-P values were affected by back transport of phosphate from shoots to roots, with a greater contribution of source P at higher temperatures when back transport was reduced. Root δ18 OTCA-P partially preserved the source signal, providing an indicator of P uptake sources. This now needs to be tested extensively for different species, soil and climate conditions to enable application in future ecosystem studies.

Phosphate distribution and sources in the waters of Huangbai River, China: using oxygen isotope composition of phosphate as a tracer.

We investigated the distributions of phosphate (PO4-P) and used the oxygen isotope composition of phosphate (δ18OP) to quantify PO4-P sources in the waters of Huangbai River. According to the environmental characteristics of Huangbai River basin, the sampling stations in the Huangbai River were divided into three groups: sampling stations in the phosphate mining area, in the outcrop area of phosphate rock, and in the residential/agricultural area. The average PO4-P concentration was highest (2.34 ± 1.00 µmol/L) in the outcrop area of phosphate ore, intermediate in the residential/agricultural area (1.06 ± 1.21 µmol/L), and lowest in the phosphate mining area (0.58 ± 0.31 µmol/L). The δ18OP measured in the Huangbai River waters ranged from 6.0 to 20.9‰, with the highest average value in the outcrop area of phosphate rock (average: 14.6‰ ± 3.1‰). The majority of the measured δ18OP values in the Huangbai River deviated greatly from the expected equilibrium values, indicating that δ18OP in this area could be used to trace PO4-P sources. We used two end-member mixing models to quantify the contribution of PO4-P from different sources. In the phosphate mining area, the average fractions of PO4-P from phosphate ore and sewage were 49.5% ± 23.8% and 50.5% ± 23.8%, respectively. In the outcrop area of phosphate rock, the average fractions of PO4-P from phosphate ore and sewage were 60.1% ± 21.7% and 39.9% ± 21.7%, respectively. In the residential/agricultural area, the average fractions of PO4-P from fertilizer and sewage were 49.2% ± 23.2% and 50.8% ± 23.2%, respectively. These results indicate that phosphate mining activities was not an important source for PO4-P in the waters of Huangbai River. The natural weathering of phosphate rock, fertilization, and domestic sewage contributed more to the high PO4-P concentrations in the Huangbai River waters.

Isotopic Traceability (13C and 18O) of Greek Olive Oil.

In recent years, isotopic analysis has been proven a valuable tool for the determination of the origin of various materials. In this article, we studied the 18O and 13C isotopic values of 210 olive oil samples that were originated from different regions in Greece in order to verify how these values are affected by the climate regime. We observed that the δ18O isotopic values range from 19.2 ‱ to 25.2 ‱ and the δ13C values range from -32.7 ‱ to -28.3 ‱. These differences between the olive oils' isotopic values depended on the regional temperature, the meteoric water, and the distance from the sea. Furthermore, we studied the 13C isotopic values of biophenolic extracts, and we observed that they have same capability to differentiate the geographic origin. Finally, we compared the isotopic values of Greek olive oils with samples from Italy, and we concluded that there is a great dependence of oxygen isotopes on the climatic characteristics of the different geographical areas.

New evidence on the earliest domesticated animals and possible small-scale husbandry in Atlantic NW Europe.

The distribution of the first domesticated animals and crops along the coastal area of Atlantic NW Europe, which triggered the transition from a hunter-gatherer-fisher to a farmer-herder economy, has been debated for many decades among archaeologists. While some advocate a gradual transition in which indigenous hunter-gatherers from the very beginning of the 5th millennium cal BC progressively adopted Neolithic commodities, others are more in favor of a rapid transition near the end of the 5th millennium caused by a further northwest migration of farmers-herders colonizing the lowlands. Here, radiocarbon dated bones from sheep/goat and possibly also cattle are presented which provide the first hard evidence of an early introduction of domesticated animals within a hunter-gatherer context in NW Belgium, situated ca. 80 km north of the agro-pastoral frontier. Based on their isotope signal it is suggested that these first domesticates were probably not merely obtained through exchange with contemporaneous farmers but were kept locally, providing evidence of small-scale local stockbreeding in the lowlands maybe as early as ca. 4800/4600 cal BC. If confirmed by future in-depth isotope analyses, the latter testifies of intense contact and transmission of knowledge in this early contact period, which is also visible in the material culture, such as the lithic and pottery technology. It also implies direct and prolonged involvement of farmer-herders, either through visiting specialists or intermarriage, which follows recent genetic evidence demonstrating much more hunter-gatherer ancestry in early farmer's genes in western Europe compared to central and SE Europe.

Specialized cattle farming in the Neolithic Rhine-Meuse Delta: Results from zooarchaeological and stable isotope (δ18O, δ13C, δ15N) analyses.

Schipluiden (3630-3380 cal BC), the earliest known year-round settlement in the Rhine-Meuse Delta in the Netherlands, is a key site for addressing the nature of Neolithic subsistence in the wetlands of northwestern Europe. A preliminary zooarchaeological study suggested that cattle husbandry was a major activity at Schipluiden. In contrast, stable carbon and nitrogen isotope analyses of human remains from the site indicated a marine-oriented diet, implying that the Mesolithic-Neolithic dietary transition continued well into the mid-4th Millennium BC in this region. Here, we re-investigate the role and nature of cattle husbandry at Neolithic Schipluiden using mortality profiles and stable isotope analysis (δ18O, δ13C, δ15N) of animal bone collagen and tooth enamel. The age-at-death analysis suggests that cattle were managed for both meat and milk production. The δ18O and δ13C analysis of tooth enamel provide evidence that calving spread over five-and-a-half-months, which would have led to a longer availability of milk throughout the year. Cattle were grazing in open, marshy environments near the site and winter foddering was practiced occasionally. The faunal isotopic data also reveal that the high 15N in human bone collagen is more likely to signal the consumption of products from cattle that grazed on 15N-enriched salt marsh plants around the site, rather than a marine-oriented diet. This undermines the previous interpretation of the dietary practices at Schipluiden by showing that human diet in mid-4th millennium BC Rhine-Meuse area was fully "Neolithic", based primarily on products from domesticates, especially cattle, with some input from wild terrestrial and aquatic resources available in their surroundings, contrary to what has been proposed before. Collating these results demonstrates a high level of investment in cattle husbandry, highlighting the social and economic importance of cattle at the lower Rhine-Meuse Delta during the 4th millennium BC.

Food Matrix Reference Materials for Hydrogen, Carbon, Nitrogen, Oxygen, and Sulfur Stable Isotope-Ratio Measurements: Collagens, Flours, Honeys, and Vegetable Oils.

An international project developed, quality-tested, and measured isotope-delta values of 10 new food matrix reference materials (RMs) for hydrogen, carbon, nitrogen, oxygen, and sulfur stable isotope-ratio measurements to support food authenticity testing and food provenance verification. These new RMs, USGS82 to USGS91, will enable users to normalize measurements of samples to isotope-delta scales. The RMs include (i) two honeys from Canada and tropical Vietnam, (ii) two flours from C3 (rice) and C4 (millet) plants, (iii) four vegetable oils from C3 (olive, peanut) and C4 (corn) plants, and (iv) two collagen powders from marine fish and terrestrial mammal origins. An errors-in-variables regression model included the uncertainty associated with the measured and assigned values of the RMs, and it was applied centrally to normalize results and obtain consensus values and measurement uncertainties. Utilization of these new RMs should facilitate mutual compatibility of stable isotope data if accepted normalization procedures are applied and documented.

Unraveling biogeochemical phosphorus dynamics in hyperarid Mars-analogue soils using stable oxygen isotopes in phosphate.

With annual precipitation less than 20 mm and extreme UV intensity, the Atacama Desert in northern Chile has long been utilized as an analogue for recent Mars. In these hyperarid environments, water and biomass are extremely limited, and thus, it becomes difficult to generate a full picture of biogeochemical phosphate-water dynamics. To address this problem, we sampled soils from five Atacama study sites and conducted three main analyses-stable oxygen isotopes in phosphate, enzyme pathway predictions, and cell culture experiments. We found that high sedimentation rates decrease the relative size of the organic phosphorus pool, which appears to hinder extremophiles. Phosphoenzyme and pathway prediction analyses imply that inorganic pyrophosphatase is the most likely catalytic agent to cycle P in these environments, and this process will rapidly overtake other P utilization strategies. In these soils, the biogenic δ18 O signatures of the soil phosphate (δ18 OPO4 ) can slowly overprint lithogenic δ18 OPO4 values over a timescale of tens to hundreds of millions of years when annual precipitation is more than 10 mm. The δ18 OPO4 of calcium-bound phosphate minerals seems to preserve the δ18 O signature of the water used for biogeochemical P cycling, pointing toward sporadic rainfall and gypsum hydration water as key moisture sources. Where precipitation is less than 2 mm, biological cycling is restricted and bedrock δ18 OPO4 values are preserved. This study demonstrates the utility of δ18 OPO4 values as indicative of biogeochemical cycling and hydrodynamics in an extremely dry Mars-analogue environment.

Strontium and oxygen isotopes as indicators of Longobards mobility in Italy: an investigation at Povegliano Veronese.

The arrival of the Longobards in Northern Italy in 568 CE marked a period of renewed political stability in the Peninsula after the collapse of the Western Roman Empire. The trajectory of the spread of Longobards in Italy across the Alps and into the South is known from many literary sources. However, their mobility and residence patterns at a population level remain to be fully understood. Here we present a multi-isotopic analysis (87Sr/86Sr and 18O/16O) of 39 humans and 14 animals buried at the Longobard necropolis of Povegliano Veronese (VR, Italy; 6th-8th century CE), to address mode and tempo of the spread of this population in the Peninsula. The geographical location of Povegliano Veronese plays a key role: the site lies along the Via Postumia, which was one of the main ancient Roman roads of Northern Italy, representing an important route in post-classical Italy. The integration of isotopic data with the archaeological evidence allowed us to determine the presence of individuals from at least three different regions of origin, building a diachronic map of the dynamics of mobility of this group in northern Italy.

Inter- and intra-tree variability of carbon and oxygen stable isotope ratios of modern pollen from nine European tree species.

Stable carbon and oxygen isotope ratios of raw pollen sampled from nine abundant tree species growing in natural habitats of central and northern Europe were investigated to understand the intra- and inter-specific variability of pollen-isotope values. All species yielded specific δ13Cpollen and δ18Opollen values and patterns, which can be ascribed to their physiology and habitat preferences. Broad-leaved trees flowering early in the year before leaf proliferation (Alnus glutinosa and Corylus avellana) exhibited on average 2.6‰ lower δ13Cpollen and 3.1‰ lower δ18Opollen values than broad-leaved and coniferous trees flowering during mid and late spring (Acer pseudoplatanus, Betula pendula, Carpinus betulus, Fagus sylvatica, Picea abies, Pinus sylvestris and Quercus robur). Mean species-specific δ13Cpollen values did not change markedly over time, whereas δ18Opollen values of two consecutive years were often statistically distinct. An intra-annual analysis of B. pendula and P. sylvestris pollen revealed increasing δ18Opollen values during the final weeks of pollen development. However, the δ13Cpollen values remained consistent throughout the pollen-maturation process. Detailed intra-individual analysis yielded circumferential and height-dependent variations within carbon and oxygen pollen-isotopes and the sampling position on a tree accounted for differences of up to 3.5‰ for δ13Cpollen and 2.1‰ for δ18Opollen. A comparison of isotope ranges from different geographic settings revealed gradients between maritime and continental as well as between high and low altitudinal study sites. The results of stepwise regression analysis demonstrated, that carbon and oxygen pollen-isotopes also reflect local non-climate environmental conditions. A detailed understanding of isotope patterns and ranges in modern pollen is necessary to enhance the accuracy of palaeoclimate investigations on δ13C and δ18O of fossil pollen. Furthermore, pollen-isotope values are species-specific and the analysis of species growing during different phenophases may be valuable for palaeoweather reconstructions of different seasons.